JP4296095B2 - Copolymer of tetrahydrofuran, ethylene oxide and additional cyclic ethers - Google Patents

Abstract

A copolymer with recurring constituent units derived by polymerizing tetrahydrofuran, ethylene oxide and at least one additional cyclic ether that can be substituted or unsubstituted that decreases the hydrophilicity imparted to the copolymer by the ethylene oxide.

Description

  The present invention relates to a novel composition comprising a copolymer of tetrahydrofuran, ethylene oxide and an additional cyclic ether.

  A homopolymer of tetrahydrofuran (THF, oxolane), ie polytetramethylene ether glycol, is well known for use as a soft segment in polyurethane. These homopolymers give excellent dynamic properties to polyurethane elastomers and fibers. They have a very low glass transition temperature, but their crystal melting temperature is higher than room temperature. Therefore, they are waxy solids at ambient temperature and need to be maintained at an elevated temperature to prevent solidification.

  Copolymerization with cyclic ethers has been used to reduce the crystallinity of polytetramethylene ether chains. This may lower the polymer melting temperature of the polyglycol and at the same time improve certain dynamic properties of polyurethanes containing such copolymers as soft segments. Comonomers used for this purpose include ethylene oxide, which can lower the copolymer melting temperature depending on the comonomer content. Also, the use of a copolymer of THF and ethylene oxide may increase certain dynamic properties of the polyurethane, such as elongation at break, which is desirable for some end uses.

  Copolymers of THF and ethylene oxide are well known in the art. Their manufacture is described, for example, in US Pat. Such a copolymer may be produced, for example, by any of the well-known methods of cyclic ether polymerization described by NPL 1. This polymerization process has catalysts with strong protic acids or Lewis acids, with heteropoly acids, and with perfluorosulfonic acid or perfluorosulfonic acid resins. In some cases, it may be advantageous to use a polymerization accelerator, such as a carboxylic acid anhydride, as described in US Pat. In these cases, the primary polymer product is a diester, which needs to be hydrolyzed in a subsequent step to obtain the desired polymer glycol.

  U.S. Patent No. 6,057,049 to Dorai discloses the production of polytetramethylene ether diesters from the polymerization of THF with one or more comonomers. Dry includes 3-methyl THF, ethylene oxide, propylene oxide, etc., but does not describe glycol copolymers of THF, ethylene oxide, and cyclic or substituted cyclic ethers.

  Glycols formed as copolymers of THF and ethylene oxide have advantages over homopolymer glycols in terms of physical properties. At ethylene oxide content greater than 20 mole percent, the copolymer glycol is a moderately viscous liquid at room temperature and has a lower viscosity than polytetrahydrofuran of the same molecular weight at temperatures above the melting point of polytetrahydrofuran. The specific physical properties of polyurethanes made from THF copolymers outweigh those polyurethanes made from THF homopolymers.

  However, there are inconveniences associated with using ethylene oxide (EO) in these copolymers. EO is very hydrophilic and may increase the water sensitivity of the corresponding polyurethane when used at the required concentration.

US Pat. No. 4,139,567 U.S. Pat. No. 4,153,786 US Pat. No. 4,163,115 US Pat. No. 5,684,179 P. "Polytetrahydrofuran" by P. Dreyfuss (Gordon & Breach, New York, 1982)

  The present invention is a copolymer glycol made by polymerizing tetrahydrofuran, ethylene oxide and at least one additional cyclic ether. The present invention also provides a polyurethane polymer comprising a reaction product of at least one organic polyisocyanate compound and a copolymer glycol prepared by copolymerizing tetrahydrofuran, ethylene oxide and at least one additional cyclic ether. It is aimed. The present invention is also directed to a spandex filament comprising the aforementioned polyurethane.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a glycol composition of interest comprising a copolymer of THF, ethylene oxide and one or more additional cyclic ethers. As used herein, the term “copolymer” means a polymer formed from at least three monomers. By introducing ethylene oxide into the polymer glycol, the hydrophilic character of the subsequent polyurethane product is increased, so that this hydrophilicity is controlled or even minimized so that the final from these copolymers. It is desirable to reduce the water sensitivity of the product produced. Additional cyclic ethers or substituted cyclic ethers are more hydrophobic and offset the increased hydrophilicity provided by the ethylene oxide comonomer. This helps to reduce the water sensitivity of compounds such as polyurethanes made from the copolymers of the present invention. Examples of such hydrophobic monomers are alkyl-substituted tetrahydrofurans that contain a smaller proportion of oxygen in the molecule than ethylene oxide and relatively large cyclic ethers. Copolymer glycols can be made containing tetramethylene oxide and ethylene oxide units in the polymer chain, and additional polyether monomer units randomly distributed along the polymer backbone. Note that alkyl-substituted oxolanes such as 3-methyloxolane are referred to as the corresponding alkyl-substituted THF, ie 3-methyl-THF in this case. The term “cyclic ether” as used herein is understood to include both unsubstituted and substituted forms.

  The copolymers of the present invention may be prepared by the procedure of Puckmayr in US Pat. No. 4,139,567 using a solid perfluorosulfonic acid resin catalyst. Alternatively, any other acidic cyclic ether polymerization catalyst may be used to produce these copolymers, such as heteropolyacids. Heteropolyacids and their salts useful in the practice of the present invention are the catalysts described for example by Aoshima et al. In US Pat. No. 4,658,065 for the polymerization and copolymerization of cyclic ethers.

  A wide range of strong acid and superacid catalysts well known to those skilled in the art can be used for the copolymerization of the cyclic ethers of the present invention. These include, but are not limited to, fluorinated sulfonic acids, supported Lewis or Bronsted acids, and various zeolites and heterogeneous acid catalysts. A group of perfluorinated ion exchange polymers (PFIEP), such as NAFION® PFIEP products, perfluorinated sulfonic acid polymers are generally suitable for use at EO levels of about 25 mol% or higher. NAFION® is an E.I. of Wilmington, Delaware. I. It is a commercial product of EI du Pont de Nemours and Company, Wilmington, DE (hereinafter, DuPont). Fluorosulfonic acid is widely used as a catalyst, especially because of the lower level of EO. Heteropolyacids (eg, phosphotungstic acid) are generally suitable for the range of EO levels used.

  The molar concentration of ethylene oxide in the polymer is 1% to 60%, preferably 1% to 30%. The molar concentration of the additional cyclic ether is 1% to 40%, preferably 1% to 20%.

  The cyclic ether can be represented by Formula 1.

Where
R is a C1-C5 alkyl or substituted alkyl group;
n is an integer having a value of 3-4 or 6-9,
m is 0 or 1, provided that when n = 4, m is 1.

  Examples of cyclic ethers are as follows:

  Although not represented by the above formula, 3,4-dimethyloxolane (3,4-dimethyl-THF) and perfluoroalkyloxiranes such as (1H, 1H-perfluoropentyl) -oxirane are used for the purposes of the present invention. It can be used as an additional cyclic substituted ether.

  The mole percent ratio of monomers in the THF / EO / 3-MeTHF copolymer is 3-50% EO, 5-25% of 3-MeTHF, with the balance being THF. A preferred mole percent range is 8-25% EO, 5-15% 3-MeTHF, and the balance THF.

  During the copolymerization process of the present invention, ethylene oxide acts as a polymerization initiator (or accelerator), the copolymerization begins by the opening of a strained three-membered ring, and the ring opening of other cyclic ethers of the present invention. To start quickly. Since a third monomer such as ethylene oxide, tetrahydrofuran, alkyl-substituted tetrahydrofuran, combines hydrophobic and hydrophilic comonomer units, careful control of the composition results in a new polymer chain. These novel copolymers are important as “soft segments” in polyurethane polymers. They are particularly important when used in the manufacture of spandex.

  “Spandex” means manufactured fibers in which the fiber-forming material is a long chain synthetic polymer comprising at least 85% by weight of segmented polyurethane. Segmented polyurethanes can be made from polymer glycols, diisocyanates, and difunctional chain extenders. In the production of spandex polymers, the polymer is extended by successive reactions of hydroxy end groups with diisocyanates and diamines. In each case, the copolymer must become a spinnable polymer with the necessary properties, such as viscosity, by chain extension.

  The polymer glycols that may be used to make the polyurethanes of the present invention can have a number average molecular weight of about 1500 to 4000. Diisocyanates that can be used include 1-isocyanato-4-[(4-isocyanatophenyl) methyl] benzene, (“4,4′-MDI”) 1-isocyanato-2-[(4-cyanatophenyl). ) Methyl] benzene (“2,4′-MDI”), a mixture of 4,4′-MDI and 2,4′-MDI, bis (4-isocyanatocyclohexyl) methane, 5-isocyanato-1- (isocyanato Methyl) -1,3,3-trimethylcyclohexane, 1,3-diisocyanato-4-methyl-benzene, and mixtures thereof. When polyurethane is desired, the chain extender is a diol, such as ethylene glycol, 1,3-propanediol, or 1,4-butanediol, and mixtures thereof.

  In some cases, monofunctional alcohol chain terminators such as butanol can be used to control the molecular weight of the polymer, and higher functionality alcohols such as pentaerythritol “chain branchers”. Can be used to control the viscosity. Such polyurethane can be melt-spun, dry-spun, or wet-spun into spandex. When polyurethaneurea (a subclass of polyurethane) is desired, the chain extender is a diamine, such as ethylenediamine, 1,3-butanediamine, 1,4-butanediamine, 1,3-diamino-2,2-dimethylbutane, 1 , 6-hexanediamine, 1,2-propanediamine, 1,3-propanediamine, N-methylaminobis (3-propylamine), 2-methyl-1,5-pentanediamine, 1,5-diaminopentane, 1,4-cyclohexane-diamine, 1,3-diamino-4-methylcyclohexane, 1,3-cyclohexane-diamine, 1,1-methylene-bis (4,4′-diaminohexane), 3-aminomethyl-3 , 5,5-trimethylcyclohexane, 1,3-diaminopentane, m-xylylenediamine, and mixtures thereof It is. Optionally, chain terminators such as diethylamine, cyclohexylamine, or n-hexylamine can be used to control the molecular weight of the polymer, and solutions using trifunctional “chain branches” such as diethylenetriamine. Viscosity can be controlled. When spandex is desired, the polyurethaneurea is typically dry spun or wet spun.

  The practice of the present invention is illustrated by the following examples, which are not intended to limit the scope of the invention.

Materials THF, 2-methyl-THF, fluorosulfonic acid, and phosphotungstic acid hydrate are available from Aldrich Chemical, Milwaukee WI, Milwaukee, Wisconsin. The phosphotungstic acid hydrate was dehydrated by heating at 300 ° C. for at least 3 hours before use.

  3-Methyl-THF, 3-ethyl-THF, and oxepane were prepared by the methods described herein.

Example 1
This example was provided to show the copolymerization of THF, 3-ethyl-THF, and ethylene oxide. THF (160 g, 2.22 mol) and 3-ethyl-THF (40 g, 0.4 mol) were added to a 500 ml 4-necked round equipped with a mechanical stirrer, dry ice cooler, thermometer, and gas inlet tube. Added to the bottom flask. 1,4-Butanediol (0.8 g, 0.01 mol) was added as a molecular weight control agent along with 10 g of dry NAFION® NR-50, which was cryogenically ground to less than 80 mesh. Neifion® NR-50 is a solid perfluorosulfonic acid resin in the form of a bead available from DuPont. The polymerization mixture was stirred and heated to 50 ° C. At this point ethylene oxide was added slowly via the gas inlet tube and continued to be added until 8.3 g (0.19 mole) was added, which took about 4 hours. The EO feed was then turned off and the gas inlet device was flushed with dry nitrogen. Heating was continued for an additional 15 minutes and then the polymerization vessel was cooled to 30 ° C. prior to filtration. The solid catalyst was recovered and could be reused. The polymer solution was vacuum dried at 100 ° C. at 0.2 mm Hg (0.027 kPa) pressure. Filtration of the final product yielded 50 g (24%) of a clear viscous polymer which was analyzed by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), and gel permeation chromatography. Characterized by (GPC). It had the following properties and composition:
Number average molecular weight: 3100
THF content: 72 mol%
EO content: 25 mol%
Content of 3-ethyl-THF: 3 mol%

Example 2
This example was provided to show the copolymerization of THF, 3-ethyl-THF, and ethylene oxide.

  A 250 ml round bottom polymerization reactor equipped with a mechanical stirrer, a dry ice reflux condenser with a Dryerite moisture barrier, a thermometer, and a gas inlet tube was prepared. THF (26 g, 0.36 mol), 3-ethyl-THF (13 g, 0.13 mol), and dry Neifion catalyst powder (brand NR-50, 3 g) were added. The mixture was heated to 60 ° C. with stirring under a slow stream of nitrogen. When the apparatus reached 60 ° C., ethylene oxide gas (EO) was slowly added through the gas inlet tube at a rate of about 6 g / hr. The EO addition was continued until a total of 6.5 g EO was added. The EO feed was then turned off and the gas inlet device was flushed with nitrogen. Heating was continued for an additional 15 minutes and then the polymerization vessel was allowed to cool to room temperature.

The polymer solution was separated from the solid catalyst by filtration, and any polymer attached to the catalyst was removed by washing with dry methanol. Unreacted monomer was removed from the solution by distillation and the polymer residue was vacuum dried at 100 ° C. and a pressure of 1 mm (0.13 kPa) of Hg for 1 hour. Final filtration yielded 36% by weight of a transparent polymer with a number average molecular weight measured by end group titration of 1075, which was the following composition when measured by NMR analysis.
49 wt% THF,
20 wt% 3-ethyl-THF and 31 wt% EO

Example 3
This example was provided to demonstrate the copolymerization of THF, oxepane, and ethylene oxide. A 100 ml round bottom polymerization reactor equipped with a mechanical stirrer, a dry ice reflux condenser with a dry alite moisture-proof tube, a thermometer, and a gas inlet tube was prepared. THF (10 g, 0.14 mol), oxepane (hexamethylene oxide, 10 g, 0.1 mol), and dry Neifion catalyst powder (brand NR-50, 2 g) were added. 1,4-butanediol was added as a molecular weight control agent. The mixture was heated to 70 ° C. with stirring under a slow stream of nitrogen. When the apparatus reached 70 ° C., ethylene oxide gas was slowly added through the gas inlet tube at a rate of 4.5 g per hour. The EO addition was continued until a total of 9 g EO was added. The EO feed was then turned off and the gas inlet device was flushed with nitrogen. Heating was continued for an additional 15 minutes and then the polymerization vessel was allowed to cool to room temperature.

The polymer solution was separated from the solid catalyst by filtration, and any polymer attached to the catalyst was removed by washing with dry methanol. The polymer was isolated from the solution by vacuum drying at 100 ° C. and a pressure of 1 mm (0.13 kPa) of Hg for 1 hour. Final filtration yielded 45% by weight of a transparent polymer having a number average molecular weight of 2420 as measured by end group titration, and had the following composition as measured by NMR analysis.
45 wt% THF,
20% by weight oxepane and 35% by weight EO

Example 4
This example was provided to show the copolymerization of THF, 3-methyl-THF, and ethylene oxide.

  THF (800 g, 11.1 mol) and 3-methyl-THF (100 g, 1.15 mol) were added to a 2 liter 4-neck round equipped with a mechanical stirrer, dry ice cooler, thermometer, and gas inlet tube. Added to the bottom polymerization reactor. 1,4-butanediol (4 g, 0.033 mol) was added as a molecular weight control agent, and dry neifion pellets (brand NR-50, 30 g) were added as a polymerization catalyst.

The polymerization mixture was stirred and heated to 50 ° C. at which time ethylene oxide was slowly added via the gas inlet tube. The ethylene oxide addition was continued until 55 g (1.25 mol) was added over about 4 hours. The ethylene oxide supply was then stopped and the gas inlet device was flushed with nitrogen. Heating was continued for an additional 15 minutes and then the polymerization vessel was cooled to 35 ° C. prior to filtration. The solid catalyst residue could be washed and recycled. The polymer solution was vacuum dried at 100 ° C. for 1 hour at a pressure of 2 mmHg (0.27 kPa). Filtration of the final product yielded a clear viscous polymer with the following representative properties.
M _n : 2700
Viscosity: 10.5 poise (1.05 Pa.s) at 40 ° C.
Melt temperature: -3.9 ° C
EO content: 28 mol%
3-methyl-THF content: 8 mol%

Examples 5-15
These examples showed the copolymerization of THF, 3-methyl-THF, and ethylene oxide using a fluorosulfonic acid (FSA) catalyst.

  The procedure for each of these examples (Table 1) is as follows. A dry baffled and jacketed glass reactor was equipped with a thermocouple, a nitrogen and ethylene oxide glass filter gas inlet, a solid carbon dioxide cooler with an outlet, and a mechanical stirrer. 3-MeTHF was added to the flask as a 55% solution of 3-MeTHF in THF with additional THF, resulting in the monomer loading shown in Table 1, and cooled to 10-15 ° C. The flask was flushed with nitrogen and fluorosulfonic acid was added dropwise through a dry addition funnel over 3-5 minutes. The reaction mass was then heated to the reaction temperature and ethylene oxide was added over about 3 hours. Agitation was performed to maintain a uniform temperature throughout the reaction mass. The temperature of the highly viscous content was raised to 45 ° C but not exceeded. The temperature was adjusted by controlling the ethylene oxide feed rate.

  To terminate and neutralize the reaction, the carbon dioxide cooler was replaced with a simple distillation head and warm water (600 mL) was added. The contents of the flask were heated to 100 ° C. to remove the THF / water distillate. The nitrogen flow was maintained to speed up the distillation. When the THF was removed, stirring was stopped and the contents were separated. The aqueous layer was removed and the organic layer was then washed twice with a 600 mL batch of hot water. After the second wash, 15 g calcium hydroxide was thoroughly stirred to allow additional water to settle and remove it. Additional calcium hydroxide was added in portions until the pH was 7-8. The polymer formulation was maintained at 80 ° C. to maintain a low viscosity.

In order to isolate the polymer, the neutralized wet polymer was stripped under vacuum at 90 ° C. Solids were removed by filtration through a diatomaceous earth mat on Whatman # 1 filter paper on a steam heated Buchner funnel. The cloudless polymer was weighed, the molecular weight was quantified by end group titration, and the composition was determined by ¹ H NMR. These data are summarized in Table 2.

Examples 16-20
These examples are provided to demonstrate the copolymerization of THF, 3-methyl-THF, and ethylene oxide using a phosphotungstic anhydride (PTA) catalyst.

A 5 L baffled, jacketed reactor was equipped with a thermocouple, ethylene oxide and nitrogen inlet, a dry ice cooler with N ₂ outlet, and a mechanical stirrer. The apparatus was dried at 100 ° C. by N ₂ washing. THF, water, and anhydrous PTA were added to the flask and cooled (see Table 3). As shown in Table 3, with additional THF, 3-MeTHF was placed in a flask as a 55% solution of 3-MeTHF in THF, resulting in monomer loadings as shown in Table 3, to 10-15 ° C. Cooled down. The reactor was flushed with nitrogen and the stirrer was set at 250 rpm. Ethylene oxide was added continuously over about 2-4 hours with cooling to maintain a specific reaction temperature. After all of the ethylene oxide had been added, stirring was continued until the total reaction time was complete. After the reaction time, 1 L of deionized water was added and the mixture was stirred at 45 ° C. for at least 30 minutes.

To purify the crude copolymer, the reaction mixture was diluted with an equal volume of methanol at 45 ° C. and the methanol solution was fed into a column packed with weak base ion exchange resin to adsorb the acid catalyst. Next, unreacted THF, methanol, and water were removed in vacuo. Solids were removed by filtration through a diatomaceous earth mat on Whatman # 1 filter paper on a steam heated Buchner funnel. The cloudless polymer was weighed, the molecular weight was quantified by end group titration, and the composition was measured by ¹ H NMR. These data are summarized in Table 4.

Example 21
This example is provided to show the copolymerization of THF, 2-methyl-THF, and ethylene oxide. A 250 ml round bottom polymerization reactor equipped with a mechanical stirrer, a dry ice reflux condenser with a dry alite moisture barrier, a thermometer, and a gas inlet tube was prepared. Tetrahydrofuran (THF, 25 g, 0.35 mol), 2-methyl-THF (75 g, 0.75 mol), and dry Neifion catalyst powder (brand NR-50, 6.5 g) were added. The mixture was heated to 60 ° C. with stirring under a slow stream of nitrogen. When the apparatus reached 60 ° C., ethylene oxide gas (EO) was slowly added through the gas inlet tube at a rate of about 6 g per hour. The EO addition was continued until a total of 17 g EO was added. The EO feed was then turned off and the gas inlet device was flushed with nitrogen. Heating was then continued for an additional 15 minutes and then the polymerization vessel was allowed to cool to room temperature.

（式中、
Ｒが、Ｃ１−Ｃ５アルキルまたは置換アルキル基であり、
ｎが、３〜４または６〜９の値の整数であり、
ｍが０または１であるが、ただし、ｎ＝４であるとき、ｍが１である）によって表さ
れる１に記載のコポリマー。
３．前記付加的な環状エーテルが、３，４−ジメチル−テトラヒドロフラン及びペルフル
オロアルキル−オキシランよりなる群から選択される１に記載のコポリマー。
４．前記付加的な環状エーテルが、オキセタン、メチル−オキセタン、ジメチル−オキセ
タン、３−メチル−テトラヒドロフラン、３−エチル−テトラヒドロフラン、２−メチ
ル−テトラヒドロフラン、オキセパン、オキソカン、オキソナン、及びオキセカンより
なる群から選択される２に記載のコポリマー。
５．酸化エチレンから誘導された構成単位のモル濃度が１パーセント〜４０パーセントで
ある１に記載のコポリマー。
６．酸化エチレンから誘導された構成単位の前記モル濃度が３パーセント〜３５パーセン
トである５に記載のコポリマー。
７．前記付加的な環状エーテルから誘導された構成単位の前記モル濃度が３パーセント〜
４０パーセントである１に記載のコポリマー。
８．前記付加的な環状エーテルから誘導された構成単位の前記モル濃度が５パーセント〜
３０パーセントである７に記載のコポリマー。
９．少なくとも１つの有機ポリイソシアネート化合物と、酸化エチレン、テトラヒドロフ
ラン及び少なくとも１つの付加的な環状エーテルを共重合させることによって誘導され
た構成単位を含んでなるコポリマーグリコールとの反応生成物を含んでなるポリウレタ
ンポリマー。
１０．前記付加的な環状エーテルが、構造

（式中、
Ｒが、Ｃ１−Ｃ５アルキルまたは置換アルキル基であり、
ｎが、３〜４または６〜９の値の整数であり、
ｍが０または１であるが、ただし、ｎ＝４であるとき、ｍが１であり、
かつ２−メチル−テトラヒドロフランを含めない）によって表される９に記載のポリウ
レタンポリマー。
１１．前記付加的な環状エーテルが、オキセタン、メチル−オキセタン、ジメチル−オキ
セタン、３−メチル−テトラヒドロフラン、３−エチル−テトラヒドロフラン、オキセ
パン、オキソカン、オキソナン、及びオキセカンよりなる群から選択される９に記載の
ポリウレタンポリマー。
１２．前記付加的な環状エーテルが、３，４−ジメチル−テトラヒドロフラン及びペルフ
ルオロアルキル−オキシランよりなる群から選択される９に記載のポリウレタンポリマ
ー。
１３．９、１０、１１、または１２に記載のポリウレタンポリマーを含んでなるスパン
デックスのフィラメント。 The polymer solution was separated from the solid catalyst by filtration, and any polymer attached to the catalyst was removed by washing with dry methanol. The polymer was isolated from the solution by vacuum drying at 100 ° C. and a pressure of 1 mm (0.13 kPa) of Hg for 1 hour. Final filtration yielded 30% by weight of a transparent polymer with a molecular weight measured by end group titration of 2000, and had the following composition as measured by NMR analysis.
25% by weight of THF,
40% by weight 2-methyl-THF and 35% by weight EO

Preferred embodiments of the present invention are as follows.

1. A copolymer comprising building blocks derived by polymerizing tetrahydrofuran, ethylene oxide and at least one additional cyclic ether.
2. The additional cyclic ether has a structure

(Where
R is a C1-C5 alkyl or substituted alkyl group;
n is an integer having a value of 3-4 or 6-9,
2. The copolymer according to 1, wherein m is 0 or 1, provided that when n = 4, m is 1.
3. The copolymer of 1, wherein the additional cyclic ether is selected from the group consisting of 3,4-dimethyl-tetrahydrofuran and perfluoroalkyl-oxirane.
4). The additional cyclic ether is selected from the group consisting of oxetane, methyl-oxetane, dimethyl-oxetane, 3-methyl-tetrahydrofuran, 3-ethyl-tetrahydrofuran, 2-methyl-tetrahydrofuran, oxepane, oxocane, oxonan, and oxecan. The copolymer according to 2, which is selected.
5. The copolymer according to 1, wherein the molar concentration of the structural unit derived from ethylene oxide is 1 percent to 40 percent.
6). 6. The copolymer according to 5, wherein the molar concentration of the structural unit derived from ethylene oxide is 3 percent to 35 percent.
7). The molar concentration of structural units derived from the additional cyclic ether is from 3 percent to
2. The copolymer of 1, which is 40 percent.
8). The molar concentration of structural units derived from the additional cyclic ether is from 5 percent to
8. The copolymer of 7, which is 30 percent.
9. Comprising a reaction product of at least one organic polyisocyanate compound and a copolymer glycol comprising structural units derived by copolymerizing ethylene oxide, tetrahydrofuran and at least one additional cyclic ether Polyurethane polymer.
10. The additional cyclic ether has a structure

(Where
R is a C1-C5 alkyl or substituted alkyl group;
n is an integer having a value of 3-4 or 6-9,
m is 0 or 1, provided that when n = 4, m is 1,
And 2-methyl-tetrahydrofuran is not included).
11. The 9 wherein the additional cyclic ether is selected from the group consisting of oxetane, methyl-oxetane, dimethyl-oxetane, 3-methyl-tetrahydrofuran, 3-ethyl-tetrahydrofuran, oxepane, oxocane, oxonan, and oxecan. Of polyurethane polymer.
12 10. The polyurethane polymer of 9, wherein the additional cyclic ether is selected from the group consisting of 3,4-dimethyl-tetrahydrofuran and perfluoroalkyl-oxirane.
A spandex filament comprising the polyurethane polymer according to 13.9, 10, 11, or 12.

Claims (4)

A copolymer comprising building blocks derived by polymerizing tetrahydrofuran, ethylene oxide and at least one additional cyclic ether , wherein the additional cyclic ether has the formula

Wherein R is a C ₁ -C ₅ alkyl or substituted alkyl group, n is 4 or an integer from 6 to 9, and m is 0 or 1, provided that when n is 4, m Is 1). The copolymer of claim 1, wherein the additional cyclic ether is selected from the group consisting of 3-methyl-tetrahydrofuran, 3-ethyl-tetrahydrofuran, 2-methyl-tetrahydrofuran, and oxepane . A polyurethane polymer comprising a reaction product of at least one organic polyisocyanate compound and the copolymer glycol according to claim 1 or 2 . Spandex filaments comprising the polyurethane polymer of claim 3 Symbol placement.